CN100379698C - Method of making coated article and resulting coated article - Google Patents

Abstract

An article comprising a first substrate, a functional coating deposited on at least a portion of the substrate, and a protective coating deposited on the functional coating. Functional and protective coatings form a coating stack. A polymeric material is deposited on at least a portion of the protective coating. The protective coating has a refractive index substantially the same as that of the polymeric material.

Description

Method of making coated article and produced coated article

Cross References to Related Applications

This application is a continuation-in-part of U.S. Application Serial No. 10/133,805 (filed April 25, 2002), which in turn is a continuation-in-part of U.S. Application Serial No. 10/007,382 (filed October 22, 2001) , which claims the benefit of US Provisional Application Serial No. 60/242,543 (filed October 24, 2000), all of which are hereby incorporated by reference in their entirety.

Background of the invention

1. Field of the invention

The present invention generally relates to coated articles, such as coated automotive transparencies, and methods of making the coated articles.

2. Description of prior art

It is known to reduce heat build-up inside a vehicle by providing a laminated windshield having two plies of glass with an infrared (IR) or ultraviolet (UV) sun-reducing coating between the plies so that Protects solar control coatings from mechanical and/or chemical damage. These common windshields are formed by forming and annealing two flat glass "blanks" (one of which has a solar control coating deposited on the surface) to form two shaped, annealed glass plies, which are then The glass plies are fixed together with a plastic interlayer to form the final product. Because common solar control coatings include metal layers that reflect heat, glass blanks are typically heated and formed as "doublets," that is, the two blanks are heated and formed one on top of the other. Placed in such a way that the functional coating is sandwiched between glass blanks to prevent uneven heating and cooling (which can affect the final shape of the ply). Examples of laminated automotive windshields and methods of making them are disclosed in US Patent Nos. 4,820,902; 5,028,759; and 5,653,903.

The heatability properties of doublets are generally limited by the ability of the functional coating to withstand heat treatment without detrimental degradation. "Heatability" means the maximum temperature and/or maximum time at a particular temperature to which the doublet can be heated without degradation of the functional coating. This degradation can take the form of oxidation of various metal layers in the coating, which can affect the optical properties of the coating, such as solar reflection and/or transmission.

It would also be desirable to provide solar control coatings on other automotive transparencies such as side windows, rear windows, sunroofs, moonroofs, and the like. However, the methods of making laminated windshields are not readily applicable to making other types of laminated and/or non-laminated automotive transparencies. For example, common automotive side windows are typically manufactured from a single glass blank that is individually heated, formed and tempered to the desired curvature determined by the size of the vehicle opening into which the side window is installed. A problem with making side windows that is not encountered when making windshields is the problem of separately heating the glass blanks with heat reflective solar control coatings.

In addition, if the side window, after positioning, requires the coating to be on the surface of the side window facing out of the vehicle (the exterior surface), the coating is susceptible to mechanical damage from objects hitting the coating and from acid rain or car washes. Chemical damage from detergents. If the coating is on the surface of the side window facing the interior of the vehicle (inner surface), the coating is susceptible to mechanical damage from being touched by a vehicle occupant or from being lifted and lowered in the window slot, as well as from contact with Chemical damage from exposure to common glass cleaners. Additionally, if the coating is a low-emissivity coating, it may contribute to the greenhouse effect, trapping heat within the vehicle.

Although it is known that chemical damage or corrosion to the coating can be reduced by overcoating a chemical resistant coating, these overcoats are typically applied as thin as possible so as not to adversely affect the optical properties of the basecoat ( such as color, reflectivity and transmittance) without significantly increasing the emissivity of the base coat. Such thin overcoats typically do not meet the shipping, processing, or end-use durability requirements of conventional coated automotive transparencies, which are susceptible to damage and continuous exposure to environmental conditions. Additionally, this thin overcoat does not mitigate the greenhouse effect problem discussed above. Examples of common overcoat coatings are disclosed in US Patent Nos. 4,716,086; 4,786,563; 5,425,861; 5,344,718; 5,376,455;

Accordingly, it would be advantageous to provide methods of making articles, such as laminated or non-laminated automotive transparencies, that have functional coatings that reduce or eliminate some of the problems discussed above.

Summary of the invention

Articles of the present invention include at least one substrate, a functional coating formed on at least a portion of the substrate, and a protective coating formed on at least a portion of the functional coating. Functional and protective coatings form a coating stack. At least one polymeric material can be formed on the protective coating. The protective coating can have a refractive index substantially the same as that of the polymeric material. Thus, there is little or no undesired optical effect, such as an undesired change in color, reflectance and/or transmission, relative to the coated substrate due to the presence of the protective coating. The article can be a laminate comprising two or more substrates, wherein the polymeric material is an interlayer material securing at least two substrates together.

Particular laminated automotive transparencies of the present invention include a first glass substrate having a first major surface and a functional coating formed on at least a portion of the first major surface. The functional coating can include at least one metal oxide-containing coating film and at least one infrared reflective metal film. A protective coating can be formed over at least a portion of the functional coating. The protective coating can comprise 0wt%-100wt% alumina, such as 5wt%-100wt%, 35wt%-100wt% alumina and/or 0wt%-100wt% silica, such as 0wt%-65wt% silica and May have a thickness between 50 Angstroms and 5 microns. The transparency further includes a second glass substrate and a polymeric material, such as but not limited to polyvinyl butyral, positioned between the protective coating and the second glass substrate. The material of the protective coating and/or polymeric material can be selected such that the refractive indices of the protective coating and the polymeric layer are substantially the same, for example within ±0.2 of each other.

The monolithic article includes a substrate, a functional coating formed on at least a portion of the substrate, and a protective coating formed on at least a portion of the functional coating. Functional and protective coatings form a coating stack. The protective coating can have a thickness between 1 micron and 5 microns. A polymeric material can be formed over at least a portion of the protective coating. The protective coating may have a refractive index substantially the same as that of the polymeric material.

A method of making a laminate comprising providing a first substrate; forming a functional coating on at least a portion of the first substrate; forming a protective coating on at least a portion of the functional coating; and forming a protective coating on at least a portion of the protective coating form a polymer material. The protective coating and/or polymeric material are selected such that the protective coating and polymeric material have substantially the same refractive index.

Another method of the present invention includes providing a first substrate, forming a functional coating on at least a portion of the first substrate, forming a protective coating on at least a portion of the functional coating, and providing a second substrate. The first and second substrates can be arranged to form a doublet with the functional coating located between the substrates. The protective coating can comprise one or more layers, for example, such as a single layer comprising 0 wt% to 100 wt% alumina and/or 100 wt% to 0 wt% silica, such as 5 wt% to 100 wt% alumina and 95 wt% to 0 wt% silica, such as 50 wt% to 70 wt% alumina and 50 wt% to 30 wt% silica. Alternatively, the protective coating can comprise two or more layers, such as comprising 5 to 100 wt % alumina and 95 to 0 wt % silica, such as 50 to 70 wt % alumina and 50 to 30 wt % A first layer of silicon, and a second layer comprising 30wt% to 100wt% silica and 70wt% to 0wt% alumina, such as 70wt% to 100wt% silica and 0wt% to 30wt% alumina. The doublet can be heated and/or shaped. The protective coating can act as an oxygen barrier to improve the heatability of the doublet by preventing or reducing oxidation of the metal layer in the underlying functional coating.

The present invention provides a method of manufacturing a laminated substrate comprising the steps of:

providing a first substrate;

forming a functional coating on at least a portion of the first substrate; and

A protective coating is formed on at least a portion of the functional coating, wherein the protective coating includes a first layer formed on the functional coating and a second layer formed on the first layer, wherein the first layer includes 50 wt% to 100 wt% alumina and 50 wt% to 0 wt% silica, and the second layer includes 50 wt% to 100 wt% silica and 50 wt% to 0 wt% alumina.

Brief description of the drawings

1 is a side sectional view (not to scale) of an edge portion of a laminated automotive transparency such as a side window incorporating the structural features of the present invention;

Figure 2 is a perspective, partial cross-sectional view of an apparatus (some parts omitted for clarity) for producing glass blank G (coated or uncoated) in the practice of the present invention;

Figure 3 is a side cross-sectional view (not to scale) of a portion of a monolith incorporating the features of the present invention;

Figure 4 is a graph showing the results of a Taber abrasion test for a substrate having a protective coating of the present invention compared to a substrate without a protective coating;

Figure 5 is a graph of average haze for selected substrates of Figure 4;

Figure 6 is a graph of emissivity values versus coating thickness for substrates having a protective coating of the present invention;

Figure 7 is a graph showing Taber Abrasion Test results for substrates having protective coatings of the present invention; and

Figure 8 is a bar graph showing the effect of heat treatment and coating thickness on Taber wear of coated substrates with protective coatings of the present invention.

Description of the preferred embodiment

As used herein, spatial or directional terms such as "left", "right", "inner", "outer", "upper", "lower", "top", "bottom", etc., refer to the The invention shown. It should be understood, however, that the invention contemplates various alternative orientations, and thus such terms are not to be considered limiting. Furthermore, as used herein, all numerical values expressing dimensions, physical properties, process parameters, ingredient amounts, reaction conditions, etc. used in the specification and claims are to be understood as being modified in all instances by the term "about" . Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims will vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Additionally, all ranges disclosed herein should be understood to include the beginning and ending range values and any sub-ranges subsumed therein. For example, a stated range of "1 to 10" should be considered to include any and all subranges between, inclusively, the lowest value of 1 and the highest value of 10; that is, starting with the smallest value of 1 or more and All subranges ending with a maximum value of 10 or less, for example, 5.5 to 10. The term "flat" or "substantially planar" substrate refers to a substrate that assumes a substantially planar form; that is, a substrate that lies primarily in a single geometric plane, as would be understood by those skilled in the art. Can include slight bends, protrusions, or depressions. In addition, the term "formed on", "deposited on", or "provided on" as used herein means formed, deposited or provided on a surface but Not necessarily in contact with the surface. For example, a coating "formed over a substrate" does not preclude the presence of one or more other coatings or films of the same or different composition located between the formed coating and the substrate. All documents herein are understood to be incorporated by reference in their entirety. As used herein, the term "polymer" or "polymeric" refers to oligomers, homopolymers, copolymers, and terpolymers, e.g., formed from two or more types of monomers or polymers polymer.

As will be appreciated from the discussion below, the protective coatings of the present invention can be used to make both laminated and non-laminated (eg, single substrate) articles. For use on laminated articles, protective coatings are generally thinner than non-laminated articles. Structural assemblies of the present invention and methods of making exemplary laminates are first described, followed by exemplary monolithic articles of the present invention. "Monolithic" means having a single structural support or structural element, eg, having a single substrate. In the following discussion, an exemplary article (whether laminated or monolithic) is described as an automotive side window. However, the present invention is not limited to automotive side windows but may be used with any article such as, but not limited to, insulating glass units, laminated windows (e.g., skylights) for residential or commercial use, or land, air, space, water and Transparent parts of underwater vehicles, such as windshields, rear windows, sun or moon roofs, just to name a few products.

Figure 1 illustrates a laminate in the form of a side window 10 incorporating the structural features of the present invention. The laminated side window 10 includes a first substrate or ply 12 having an exterior major surface 13 and an interior major surface 14 . "Ply" means a substrate that has been bent to a desired shape or curvature and/or has been heat treated (eg, by annealing or tempering). Functional coating 16 can be deposited on interior major surface 14 by any conventional means, such as but not limited to chemical vapor deposition, magnetron sputtering vapor deposition, spray pyrolysis (to name a few), such as on It is formed on at least a part of the surface, preferably on the entire surface. As will be described in more detail, the protective coating 17 of the present invention can be formed on the functional coating 16, for example on at least a part thereof, preferably on all of it, not only contributes to improving mechanical and chemical stability, but also provides improved heating characteristics for bending and/or forming blanks on which the coating has been deposited. Polymer layer 18 can be positioned between first ply 12 and a second substrate or ply 20 having an inner major surface 22 and an outer major surface 23 . In one non-limiting embodiment, major surface 23 can face the exterior of the vehicle and exterior major surface 13 can face the interior of the vehicle. A conventional edge sealant 26 can be applied to the periphery of the laminated side window 10 during and/or after lamination in any conventional manner. A decorative strip 90, such as an opaque, translucent or colored strip, such as a ceramic strip, can be provided on the surface of at least one of the plies 12 and 20, such as around the circumference of one of the interior or exterior major surfaces.

In a broad practice of the invention, the substrates for the first ply 12 and the second ply 20 can be any desired material having any desired properties such as being opaque, translucent or transparent to visible light. "Transparent" means greater than 0% to 100% transmittance through the substrate. "Visible light" or "visible spectral region" refers to electromagnetic energy between 395 nanometers (nm) and 800 nm. Alternatively, the substrate can be translucent or opaque. "Translucent" means allowing electromagnetic energy (eg, visible light) to pass through a substrate but scattering this energy so that objects are not clearly visible on the side of the substrate opposite the observer. "Opaque" means having 0% visible light transmission. Examples of suitable substrates include, but are not limited to, plastic substrates (such as acrylic polymers, such as polyacrylates; polyalkylmethacrylates, such as polymethylmethacrylate, polyethylmethacrylate, poly Propyl methacrylate, etc.; Polyurethanes; Polycarbonates; Polyalkylene terephthalates such as polyethylene terephthalate (PET), Polytrimethylene terephthalate, Polyterephthalate Butylene dicarboxylate, etc.; polysiloxane-containing polymers; or copolymers of any of the monomers used to make these, or any mixture thereof); metal substrates such as, but not limited to, galvanized steel , stainless steel, and aluminum; ceramic substrates; ceramic tile substrates; glass substrates; or mixtures or combinations of any of the above substrates. For example, the substrate can be plain unpigmented soda lime-silica-glass, i.e., "clear glass", or can be tinted or otherwise tinted glass, borosilicate glass, leaded glass, tempered , Untempered, annealed or heat-treated glass. The glass may be of any type, such as ordinary float glass or flat glass, and may have any optical properties (for example, any value of visible radiation transmittance, ultraviolet radiation transmittance, infrared radiation transmittance, and/or total solar radiation transmittance). Energy transmittance) any composition. Types of glasses suitable for the practice of the present invention are described, for example and not considered limiting, in U.S. Patent Nos. 4,746,347; 4,792,536; 5,240,886; 5,385,872; and 5,393,593. The invention is not limited by the thickness of the substrate. The substrate is generally used at a greater thickness in typical architectural applications than in typical vehicular applications. In one embodiment, the substrate can be glass with a thickness in the range of 1 mm to 20 mm, such as about 1 mm to 10 mm, such as 2 mm to 6 mm, such as 3 mm to 5 mm. To form a laminated automotive side window, the first and second plies 12, 20 can be less than about 3.0 mm thick, such as less than about 2.5 mm thick, such as in the range of about 1.0 mm to about 2.1 mm thick. As described below, the substrate can be thicker for monolithic articles.

The functional coating 16 can be of any desired type. As used herein, the term "functional coating" refers to a coating that improves one or more physical properties (e.g., optical, thermal, chemical or mechanical properties) completely removed from the substrate during the process. The functional coating 16 can have one or more functional coatings or films having the same or different composition or function. As used herein, the term "film" refers to the desired or selected area of application of the coating composition. A "layer" can comprise one or more "films" and a "coating" can comprise one or more "layers".

For example, the functional coating 16 can be a conductive coating such as those disclosed in US Pat. Layer film coating. Likewise, the functional coating 16 can be a solar control coating. As used herein, the term "sun control coating" refers to a coating consisting of one or more layers or films that affect the solar properties of a coated article, such as, but not limited to, the amount of solar radiation, such as Visible light, infrared light or ultraviolet radiation on and/or passing through the coated article, infrared or ultraviolet absorption or reflection, shading coefficient, emissivity, etc. The solar control coating is capable of shading, absorbing or filtering selected portions of the solar spectrum, such as but not limited to the IR, UV, and/or visible spectrum. Examples of solar control coatings that can be used in the practice of the present invention are, for example but not considered limiting, in US Patent Nos. 4,898,789; 5,821,001; 4,716,086; 4,610,771; and 5,028,759, and found in US Patent Application Serial No. 09/058,440.

The functional coating 16 may also be a low emissivity coating that allows visible wavelength energy (eg, 395nm to 800nm) to pass through the coating but reflects longer wavelength solar infrared energy. "Low emissivity" means an emissivity lower than 0.4, such as lower than 0.3, such as lower than 0.2, such as lower than 0.1, eg, less than or equal to 0.05. Examples of low emissivity coatings are found, for example, in US Patent Nos. 4,952,423 and 4,504,109 and British Reference GB 2,302,102. The functional coating 16 can be a single-layer coating or a multi-layer coating and can include one or more metals, non-metals, semi-metals, semiconductors, and/or alloys, composites, composite materials, combinations, or blends. For example, the functional coating 16 can be a single-layer metal oxide coating, a multi-layer metal oxide coating, a non-metal oxide coating, a metal nitride or oxynitride coating, or a non-metal nitride or oxynitride coating. Compound coating, or multi-layer coating.

Examples of suitable functional coatings for use in the present invention are commercially available from PPG Industries, Inc. of Pittsburgh, Pennsylvania as the SUNGATE(R) and SOLARBAN(R) families of coatings. Such functional coatings typically include one or more antireflective coating films, which include dielectric or antireflective materials, such as oxides of metal oxides or metal alloys, which are transparent to visible light. The functional coating may also include one or more infrared reflective films comprising reflective metals, for example, noble metals such as gold, copper or silver, or combinations or alloys of these metals, and can further include Primer films or barrier films known in the prior art, such as titanium films, above and/or below. The functional coating can have any desired number of infrared reflective films, such as 1 or more silver layers, eg, 2 or more silver layers, eg, 3 or more silver layers.

Although not limiting to the present invention, the functional coating 16 can be located on one of the interior major surfaces 14, 22 of the laminate such that it would be the same as if the functional coating 16 were located on the outer surface of the laminate. Rather, the coating 16 is less susceptible to environmental and mechanical wear. The functional coating 16 may however also be provided on one or both of the outer major surfaces 13 or 23 . As shown in FIG. 1 , a portion of the coating 16, for example, about 1 mm to 20 mm around the outer periphery of the coated area, such as a 2 mm to 4 mm wide area, can be removed or removed in any conventional manner, such as by Grinding prior to lamination or masking during coating minimizes damage to the functional coating 16 on the edges of the laminate caused by weathering or environmental effects during use. In addition, removal is performed for functional properties, for example, for an antenna, for electrically heating a windshield, or for improving radio wave propagation, and the removed portion can have any size. For aesthetic purposes, colored, opaque or translucent strips 90 can be provided on any surface of the plies or coatings, such as on one or both surfaces of one or both plies, such as on the outer major surface 13 Around the circumference of the , to cover the part that should be removed. Strip 90 can be manufactured from a ceramic material and can be fired on outer major surface 13 in any conventional manner.

The protective coating 17 of the present invention can be formed on, for example, at least a part of, preferably the entire outer surface of the functional coating 16 . In particular the protective coating 17 is capable of increasing the emissivity of the coating stack (eg the functional coating plus protective coating) greater than the emissivity of the functional coating 16 alone. For example, if the functional coating 16 has an emissivity value of 0.2, the addition of the protective coating 17 can increase the emissivity value of the formed coating stack to an emissivity value greater than 0.2. In one embodiment, the protective coating is capable of increasing the emissivity of the resulting coating stack by a factor of 2 or more compared to the emissivity of the functional coating alone (e.g., if the emissivity of the functional coating If the emissivity is 0.05, the addition of the protective layer can increase the emissivity of the resulting coating stack to 0.1 or more), such as to 5 times or more, for example, to 10 times or more, for example, Increased to 20 times or more. In another embodiment of the invention, the protective coating 17 is capable of increasing the emissivity of the resulting coating stack to substantially the same as the emissivity of the substrate on which the coating is deposited, e.g., by the difference in the emissivity of the substrate within 0.2 of. For example, if the substrate is glass having an emissivity of about 0.84, the protective coating 17 can provide an emissivity between 0.3 and 0.9, such as greater than 0.3, such as greater than 0.5, such as greater than 0.6, such as between 0.5 and Between 0.9, the coating stack. As described below, increasing the emissivity of functional coating 16 by deposition of protective coating 17 can improve the heating and cooling characteristics of coated ply 12 during processing. The protective coating 17 also protects the functional coating 16 from mechanical and chemical damage during handling, storage, transportation and processing.

In one embodiment, the protective coating 17 can have a refractive index (ie, a refractive index) that is substantially the same as that of the ply 12 to which the coating is laminated. For example, if the layer 12 is glass with a refractive index of 1.5, the protective coating 17 can have a refractive index lower than 2, such as 1.3 to 1.8, eg, 1.5±0.2.

The protective coating 17 can have any desired thickness. In an exemplary laminate example, the protective coating 17 can have an thickness of. Furthermore, this protective coating 17 can have a non-uniform thickness over the entire surface of the functional coating 17 . "Non-uniform thickness" means that the thickness of the protective coating 17 can vary over a given unit area, eg the protective coating 17 can have high and low spots or areas.

The protective coating 17 can be any desired material or a mixture of these materials. In an exemplary embodiment, the protective coating 17 can include one or more metal oxide materials such as, but not limited to, alumina, silica, or mixtures thereof. For example: the protective coating can be a single coating comprising 0 to 100 wt% alumina and/or 0 to 100 wt% silica, such as 5 to 100 wt% alumina and 95 to 0 wt% silica , such as 10wt% to 90wt% alumina and 90wt% to 10wt% silica, such as 15wt% to 90wt% alumina and 85wt% to 10wt% silica, such as 15wt% to 70wt% alumina and 85wt% to 30wt% % silica, such as 50wt% to 70wt% alumina and 50wt% to 30wt% silica, such as 35wt% to 100wt% alumina and 65wt% to 0wt% silica, for example, 70wt% to 90wt% alumina and 10wt% to 30wt% silica, e.g., 75wt% to 85wt% alumina and 15wt% to 25wt% silica, e.g., 88wt% alumina and 12wt% silica, e.g., 65wt% to 75wt% Alumina and 25wt% to 35wt% silica, for example, 70wt% alumina and 30wt% silica. Other materials, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium, and/or oxides thereof, may also be present.

Alternatively, the protective coating 17 can be a multi-layer coating consisting of layers of a metal oxide material formed separately, such as but not limited to a bi-layer consisting of a layer comprising a metal oxide. (eg, a first layer comprising silica and/or alumina) is formed over another metal oxide-containing layer (eg, a second layer comprising silica and/or alumina). The individual layers of the multilayer protective coating 17 can have any desired thickness.

The protective coating may have a thickness between 1 micron and 5 microns.

In one embodiment, the protective coating 17 can include a first layer formed on the functional coating and a second layer formed on the first layer. In one non-limiting embodiment, the first layer can comprise alumina or a mixture or alloy comprising alumina and silica. For example, the first layer can comprise a material having greater than 5 wt% alumina, such as greater than 10 wt% alumina, such as greater than 15 wt% alumina, such as greater than 30 wt% alumina, such as greater than 40 wt% alumina, such as 50 wt% to 100 wt% alumina and 50wt% to 0wt% silica, such as 50wt% to 70wt% alumina, such as between 70wt% to 100wt% alumina and between 30wt% to 0wt% silica for silica/alumina mixture. In a non-limiting embodiment, the first layer can have a thickness greater than 0 angstroms to 1 micron, such as 50 angstroms to 1 micron, such as 50 angstroms to 100 angstroms, such as 100 angstroms to 250 angstroms, such as 101 Angstrom to 250 Angstrom, such as 100 Angstrom to 150 Angstrom, such as greater than the thickness of 100 Angstrom to 125 Angstrom. The second layer can comprise silica or a mixture or alloy comprising silica and alumina. For example, the second layer can comprise silica having greater than 40 wt%, such as greater than 50 wt% silica, such as greater than 60 wt% silica, such as 70 wt% to 100 wt% silica and 30 wt% to 0 wt% alumina, such as greater than 70wt% silica, such as greater than 80wt% silica, such as between 80wt% and 90wt% silica and between 10wt% and 20wt% alumina, for example, 85wt% silica and 15wt% A silica/alumina mixture of alumina. In a non-limiting embodiment, the second layer can have a thickness between greater than 0 angstroms to 2 microns, such as 50 angstroms to 5,000 angstroms, such as 50 angstroms to 2,000 angstroms, such as 100 angstroms to 1,000 angstroms, such as 300 angstroms to 1,000 angstroms 500 angstroms, such as a thickness of 350 angstroms to 400 angstroms. As described below, the presence of the protective coating 17 can improve the heatability of the functionally coated substrate.

Polymer layer 18 can comprise any polymeric material. A "polymeric material" can comprise one polymeric component or can comprise a mixture of different polymeric components, such as but not limited to one or more plastics, such as but not limited to one or more thermoset or thermoplastic materials. This polymer layer 18 is capable of bonding the plies together. Useful thermoset components include polyesters, epoxies, phenolic resins, and polyurethanes such as reaction injection molded polyurethane (RIM) thermosets and mixtures thereof. Useful thermoplastic materials include thermoplastic polyolefins such as polyethylene and polypropylene, polyamides such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, acrylic polymers, vinyl polymers, polycarbonate, acrylonitrile-butadiene-styrene (ABS) copolymer, EPDM rubber, and their copolymers and mixtures.

Suitable acrylic polymers include acrylic acid, methacrylic acid and their alkyl esters such as methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, ethyl acrylate, hydroxy acrylate A copolymer of one or more of ethyl ester, butyl acrylate and 2-ethylhexyl acrylate. Other suitable acrylic polymers and methods of making them are disclosed in US Patent No. 5,196,485.

Useful polyester and alkyd resins can be prepared in a known manner from polyols such as ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane and pentaerythritol, with polyols Prepared by condensation of carboxylic acids such as adipic acid, maleic acid, fumaric acid, phthalic acid, trimellitic acid or drying oil fatty acids. Examples of suitable polyester materials are disclosed in US Patent Nos. 5,739,213 and 5,811,198.

Useful polyurethanes include polymer polyols such as polyester polyols or acrylic polyols with polyisocyanates, including aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanates, and cycloaliphatic diisocyanates such as the reaction product of isophorone diisocyanate and 4,4'-methylene bis(cyclohexyl isocyanate). The term "polyurethane" as used herein shall include polyurethanes and polyureas, and poly(urethane-ureas).

Suitable epoxy functional materials are disclosed in US Patent No. 5,820,987. Useful vinyl resins include polyvinyl acetal, polyvinyl formal, and polyvinyl butyral.

The polymer layer 18 can have any desired thickness, for example, in one non-limiting embodiment the thickness can range from 0.50 mm to about 0.80 mm, such as 0.76 mm for polyvinyl butyral. The polymeric material can have any desired refractive index. In one embodiment, the polymeric material has a refractive index between 1.4 and 1.7, such as 1.5 to 1.6.

The protective coating 17 can have substantially the same refractive index as the material of the polymer layer 18 . "Substantially the same" refractive index means that the protective coating material and the polymer layer material have the same or close enough refractive indices that the presence of the protective coating 17 will cause little or no undesirable Optical effects such as undesired changes in color, reflectivity or transmittance. In effect, the protective coating 17 behaves optically as if it were a continuation of the polymer layer material. The presence of protective coating 17 preferably does not lead to the introduction of an optically undesirable interface between protective coating 17 and polymer layer 18 . In one embodiment, the protective coating 17 and the polymer layer 18 can have a refractive index that differs from each other within ±0.2, such as within ±0.1, such as within ±0.05. Provided the protective coating material has the same or substantially the same refractive index as the polymer layer material, the presence of the protective coating 17 does not negatively affect the optical properties of the laminate as compared to a laminate without the protective coating 17. Optical properties of laminated products. For example, if the polymer layer 18 comprises polyvinyl butyral with a refractive index of 1.5, then the protective coating 17 can have a refractive index below 2, such as 1.3 to 1.8, eg, 1.5±0.2 after selection or formation. An exemplary method of manufacturing a laminated side window 10 employing the structural features of the present invention is now discussed below.

A first substrate and a second substrate are provided. The first and second substrates can be planar glass blanks having a thickness of about 1.0 mm to 6.0 mm, typically about 1.0 mm to about 3.0 mm, such as about 1.5 mm to about 2.3 mm. Functional coating 16 can be formed on at least a portion of a major surface (eg, major surface 14 ) of the first glass substrate. The functional coating 16 can be formed in any conventional manner, such as, but not limited to, magnetron sputtering vapor deposition (MSVD), pyrolytic deposition such as chemical vapor deposition (CVD), spray pyrolysis, atmospheric pressure CVD ( APCVD), low pressure CVD (LPCVD), plasma enhanced CVD (PEVCD), plasma assisted CVD (PACVD), or thermal evaporation by resistive or electron beam heating, cathodic arc deposition, plasma spray deposition, wet chemical deposition deposition (eg, sol-gel, mirror silvering, etc.), or any other desired means. For example, the functional coating 16 can be formed on the first substrate after the first substrate is cut to the desired size. Alternatively, the functional coating 16 can be formed on the glass sheet prior to glass sheet processing and/or supported on molten metal in a conventional pontoon using one or more conventional CVD coaters located in the pontoon. For example a bath of tin is formed on a strip of float glass. After leaving the buoyancy tank, the strip can be trimmed to form a coated first substrate.

Alternatively, the functional coating 16 can be formed on the float glass strip after the strip leaves the buoyancy tank. For example, U.S. Patent Nos. 4,584,206, 4,900,110 and 5,714,199 disclose methods and apparatus for depositing metal-containing films on the bottom surface of glass ribbons. Known devices are able to be located downstream of the molten tin bath in the float glass production process in order to obtain a functional coating on the bottom of the glass ribbon, ie on the side of the ribbon that is in contact with the molten metal. Still further, the functional coating 16 can be formed by MSVD on the first substrate after the substrate has been cut to the desired size.

The protective coating 17 of the present invention can be formed on at least a portion of the functional coating 16 . The protective coating 17 provides several processing advantages in the manufacture of laminates. For example, protective coating 17 also protects functional coating 16 from mechanical and/or chemical damage during handling, shipping, storage, shipping and processing. Additionally, the protective coating 17 can facilitate the individual heating and cooling of the functionally coated blank by increasing the emissivity of the resulting coating stack, as described below. Although topcoats have been applied over functional coatings in the past to help protect the functional coating from chemical and mechanical damage during processing, these topcoats are made as thin as possible so as not to compromise functionality Aesthetics or solar control properties of permanent coatings, such as coating emissivity. In contrast, in the present invention, the protective coating 17 can be made thick enough to increase the emissivity of the coating stack. Furthermore, the presence of protective coating 17 contributes to the aesthetics of laminate 10 by substantially matching the refractive index of protective coating 17 to that of the polymeric layer 18 material (and/or the substrate to which it is laminated). and/or optical properties with little or no adverse effect.

If the functional coating 16 is a low-emissivity coating with one or more infrared reflective metal layers, adding a protective coating 17 to increase the emissivity of the coating stack will reduce the thermal infrared of the functional coating 16. reflective properties. However, the coating stack retains solar infrared reflectivity.

The protective coating 17 can be formed in any conventional manner, such as but not limited to those methods described above for applying functional coatings, such as in-bath or out-of-bath CVD, MSVD or sol-gel methods, to name a few Just an example. For example, a substrate with a functional coating can be directed into a conventional MSVD coating apparatus having one or more metal electrodes, such as a cathode, which can be sputtered in an oxygen-containing atmosphere to form a protective metal oxide coating . In a non-limiting embodiment, the MSVD device can include one or more cathodes of aluminum, silicon, or a mixture or alloy of aluminum or silicon. The cathode can be, for example, 5wt% to 100wt% aluminum and 95wt% to 0wt% silicon, such as 10wt% to 100wt% aluminum and 90wt% to 0wt% silicon, such as 35wt% to 100wt% aluminum and 0wt% % to 65 wt% silicon, eg, 50 wt% to 80 wt% aluminum and 20 wt% to 50 wt% silicon, eg, 70 wt% aluminum and 30 wt% silicon. Additionally, other materials or dopants, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium or zirconium, may also be present to facilitate sputtering of the cathode and/or to affect the refractive index or durability. As noted above, protective coating 17 can be formed as a single layer comprising one or more metal oxide materials or as a multilayer coating having two or more individual layers, each individual layer comprising one or more Various metal oxide materials. The protective coating 17 can be applied in sufficient amount or to a sufficient thickness to increase the emissivity of the coating stack above that of the functional coating alone. In one embodiment, the protective coating can be applied to a thickness in the range of 100 Angstroms to 50,000 Angstroms and/or to increase the emissivity of the coating stack to greater than or equal to about 0.3, for example, greater than or equal to 0.4, for example , greater than or equal to 0.5.

The functional coating 16 and/or protective coating 17 can be applied to a flat substrate or to the substrate after it has been bent and shaped to the desired profile.

The coated first substrate and the uncoated second substrate can be cut to obtain a first coated portion and a second uncoated portion, respectively, each having a desired shape and a desired size. The coated and uncoated plies can be stitched, washed, bent and formed to desired contours to form the laminated first and second plies 12 and 20, respectively. Those skilled in the art will recognize that the overall shape of the coated and uncoated blanks and plies depends on the particular vehicle into which they are introduced, since the final shape of the side windows varies between different automobile manufacturers.

Coated and uncoated blanks can be formed using any desired process. For example, the blank can be formed using the "RPR" process disclosed in US Patent No. 5,286,271 or the modified RPR process disclosed in US Patent Application Serial No. 09/512,852. Figure 2 shows an additional RPR apparatus 30 suitable for use in the practice of the present invention and includes a furnace 32, such as a radiant heat furnace or a tunnel annealing furnace (Lehr), having a furnace conveyor consisting of a plurality of spaced apart furnace conveyor rollers 36 34. Heaters, such as radiant heating coils, can be distributed along the length of the furnace 32 above and/or below the furnace conveyor 34 and can be controlled to form heating zones of different temperatures along the length of the furnace 32 .

The forming station 50 can be located near the discharge end of the furnace 32 and can include a lower mold 51 having a vertically moveable flexible ring 52 and a forming station conveyor 54 having a plurality of rollers 56 . An upper vacuum mold 58 having a removable or reconfigurable molding surface 60 of a predetermined shape can be positioned above the lower mold 51 . The vacuum mold 58 can be moved via a shuttle arrangement 61 .

A transfer station 62 having a plurality of formed transfer rolls 64 can be located near the discharge end of the forming station 50 . The transfer roll 64 can have a lateral elevational curvature substantially corresponding to the lateral curvature of the forming surface 60 .

A tempering or cooling station 70 can be located near the discharge end of the transfer station 62 and can include a plurality of rollers 72 for conveying the billet through the station 70 for cooling, tempering, and/or thermal enhancement. The roller 72 can have a transverse elevation curvature substantially the same as the transverse curvature of the transfer roller 64 .

In the past, difficulties have arisen in heating functionally coated blanks (substrates) due to the heat reflection of the functional coating 16, which causes uneven heating of the coated and uncoated sides of the blanks. US Patent Application Serial No. 09/512,852 discloses a method of overcoming this problem by modifying the RPR heating process to supply heat primarily to the non-functional coating surface of the blank. In the present invention, this problem is solved by the deposition of an emissivity-enhancing protective coating 17 which allows the same or substantially the same heating process to be used for both functionally coated and non-functionally coated blanks.

As shown in FIG. 2, a first blank 80 having a coating stack (e.g., functional coating 16 and protective coating 17) and a non-functional coating second blank 82 can be heated, shaped, and cooled separately, This is followed by lamination. "Separately heated" means that the billets are not stacked one on top of the other during heating. In one embodiment, the first billet 80 is placed on the furnace conveyor 34 with the protective coating 17 facing down, ie, in contact with the furnace conveyor rollers 36, during the heating process. The presence of the higher emissivity protective coating 17 reduces thermal reflectivity problems due to the metallic layer of the functional coating 16 and promotes more uniform heating of the coated and uncoated sides of the first blank 80 . This helps prevent curling of the first blank 80 that is common during previous heating processes. In an exemplary embodiment, the billet is heated to a temperature of about 640°C to 704°C for a period of about 10 minutes to 30 minutes.

At the end of the furnace 32 , the softened glass blank, whether coated 80 or uncoated 82 , moves from the furnace 32 into the forming station 50 and onto the lower mold 51 . The lower mold 51 moves upward, lifting the glass blank to press the heat-softened glass blank against the forming surface 60 of the upper mold 58 such that the glass blank follows the shape, eg curvature, of the forming surface 60 . The upper surface of the glass blank is in contact with the forming surface 60 of the upper mold 58 and held in place by the vacuum.

Activation of the shuttle array 61 moves the upper vacuum mold 58 from the forming station 50 to the transfer station 62 at which point the vacuum is interrupted to release the formed glass blank onto curved transfer rolls 64 . The transfer rolls 64 move the shaped glass blank onto the rolls 72 and into the cooling station 70 for tempering or heat strengthening in any suitable manner. In the cooling station 70, air is directed above and below the formed glass blank to temper or heat strengthen the glass blank to form the first and second plies 12 and 20. The presence of the high-emissivity protective coating 17 also promotes more uniform cooling of the coated blank 80 in the cooling station 70 .

In another embodiment, the coated and uncoated blanks are heated and/or shaped as a doublet. In one embodiment, the coated and uncoated blanks are positioned such that the functional coating 16 with the protective coating 17 is between the two blanks. The blank is then heated and/or shaped in any conventional manner. It is believed that the protective coating 17 acts as an oxygen barrier to reduce or prevent the ingress of oxygen into the functional coating 16 where the oxygen can interact with components of the functional coating 16 such as but not limited to metals (e.g., silver) to degrade the functional coating 16. In one conventional method, the doublet can be placed on a carrier and heated to a temperature sufficient to bend or form the blank to the desired final profile. In the absence of protective coating 17, a typical functionally coated blank cannot withstand a heating cycle of heating above about 1100°F (593°C) for more than about two minutes without degradation of functional coating 16 (during which heating During the cycle, heat to above 900°F (482°C) for about 6 minutes or more). Possible forms of this degradation are a hazy or yellowish appearance with a reduction in visible transmission of 10% or more. The metal layer in the functional coating 16 , such as a silver layer, is capable of reacting with oxygen diffused into the functional coating 16 or oxygen present in the functional coating 16 . However, it is believed that the use of the protective coating 17 will allow the functionally coated blank to withstand a temperature of 1100°F (593°C) or higher for a period of five to fifteen minutes, such as five to ten minutes, such as five to ten minutes. A six-minute heating cycle (in which the heating cycle is heated to above 900°F (482°C) for ten to twenty minutes, such as ten to fifteen minutes, such as ten to twelve minutes), has no significant effect on the functional coating 16. Degradation, such as less than 5% loss in visible light transmission, such as less than 3% loss, such as less than 2% loss, such as less than 1% loss, such as no visible light transmission loss.

To form the laminate 10 of the present invention, the coated glass ply 12 is positioned such that the coated interior major surface 14 faces the substantially complementary interior major surface 22 of the uncoated ply 20 and is polymerized The material layer 18 is separated therefrom. A portion of this coating 16 and/or protective coating 17 , for example a band of about 2 mm width, can be removed from around the circumference of the first ply 12 before lamination. The ceramic tape 90 can be provided on one or both of the plies 12 or 20, for example, on the outer surface 13 of the first ply 12, to conceal the uncoated peripheral area of the laminated side window and/or provide a Occupants inside the vehicle provide additional shading. The first ply 12, the polymeric layer 18 and the second ply 20 can be laminated in any suitable manner, such as, but not limited to, as disclosed in US Patent Nos. 3,281,296; 3,769,133; and 5,250,146 Together, the laminated side window 10 of the present invention is formed. Edge sealant 26 can be applied to the edge of side window 10 as shown in FIG. 1 .

Although the above method of forming the laminated side window 10 of the present invention employs RPR apparatus and methods, the side window 10 of the present invention can be formed by other methods, such as disclosed in, for example, US Patent Nos. 4,661,139; 4,197,108; 4,272,274; 4,265,650; 4,830,650; 3,459,526; 3,476,540; 3,527,589; and 4,579,577 for the horizontal press bending method.

Figure 3 shows a monolith 100, in particular a monolithic automotive transparency, incorporating the structural features of the present invention. The article 100 includes a substrate or ply 102 having a first major surface 104 and a second major surface 106 . The functional coating 108 can be formed over at least a portion, such as over a majority, eg over all, of the surface area of the first major surface 104 . The protective coating 110 of the present invention can be formed over at least a portion, such as a majority, for example all, of the surface area of the functional coating 108 . Functional coating 108 and protective coating 110 can be formed in any desired method, such as those described above. The functional coating 108 and the protective coating 110 constitute a coating stack 112 . The coating stack 112 can include other coatings or films such as, but not limited to, conventional color suppression layers or sodium ion diffusion barrier layers, just to name a few. An optional polymeric layer 113, such as those comprising one or more polymeric materials such as those described above, can be deposited over protective coating 110 in any desired manner.

The ply 102 can be of any desired material, such as those described above for the plies 12, 20, and can be of any desired thickness. In a non-limiting embodiment used as a full-body automotive side window, the ply 102 can have a thickness of less than or equal to 20mm, for example, less than about 10mm, such as about 2mm to about 8mm, for example, about 2.6mm to about 6mm thickness of.

Functional coating 108 can be of any desired type or thickness, such as those described above for functional coating 16 . In one embodiment, the functional coating 108 is a solar control coating having a thickness of about 600 Angstroms to about 2400 Angstroms.

Protective coating 110 can be of any desired material and have any desired structure, such as those described above for protective coating 17 . The protective coating 110 of the present invention can be formed in an amount sufficient to increase (eg, significantly increase) the emissivity of the coating stack 112 beyond that of the functional coating 108 alone. For an exemplary monolithic article, protective coating 110 can have a thickness greater than or equal to 1 micron, such as between 1 micron and 5 microns. In one embodiment, the protective coating 110 increases the emissivity of the coating stack 112 by at least a factor of 2 compared to the emissivity of the functional coating 108 alone (i.e., if the emissivity 108 of the functional coating 108 is 0.05, the addition of the protective coating 110 increases the emissivity of the formed coating stack 112 to at least 0.1). In another embodiment, protective coating 110 increases emissivity by at least a factor of 5, such as by a factor of 10 or more. In yet another embodiment, the protective coating 110 increases the emissivity of the coating stack 112 to 0.5 or more, such as greater than 0.6, such as between about 0.5 and about 0.8.

Increasing the emissivity of the coating stack 112 can maintain the solar reflectivity of the functional coating 108 (e.g., reflectance of electromagnetic energy in the range of 700 nm to 2100 nm) but reduce the thermal energy reflectivity of the functional coating 108 (e.g., , the reflectivity of electromagnetic energy in the range of 5000nm to 25,000nm). Increasing the emissivity of functional coating 108 through the formation of protective coating 110 also improves the heating and cooling characteristics of the coated substrate during processing, as described above in discussing the laminate. The protective coating 110 also protects the functional coating 108 from mechanical and chemical damage during handling, storage, transportation and processing.

The protective coating 110 can have a refractive index that is the same or substantially the same as that of the ply 102 on which the coating is deposited. For example, if the ply 102 is glass with a refractive index of 1.5, the protective coating 110 can have a refractive index lower than 2, such as 1.3 to 1.8, eg, 1.5±0.2. Alternatively or additionally, protective coating 110 can have a refractive index that is substantially the same as that of polymeric layer 113 .

Protective coating 110 can have any thickness. In one monolithic example, protective coating 110 can have a thickness of 1 micron or more to reduce or prevent color changes in the appearance of article 100 . The protective coating 110 can have a thickness below 5 microns, such as between 1 and 3 microns. In one embodiment, the protective coating 110 can be thick enough to pass the common ANSI/SAE 26.1-1996 test with less than 2% gloss loss over 1000 revolutions for use as an automotive Transparent pieces. Protective coating 110 does not have to be of uniform thickness across the entire surface of functional coating 108, but has high and low spots or areas.

Protective coating 110 can be a single layer comprising one or more metal oxide materials, such as those described above. Alternatively, protective coating 110 can be a multilayer coating having two or more coatings (as described above). Each coating can include one or more metal oxide materials. For example, in one embodiment, protective coating 110 can include a first layer comprising alumina and a second layer comprising silica. Each coating can be of any desired thickness, as described above.

The substrate with coating stack 112 can be heated and/or shaped in any desired manner, as described above for the coated stock of the laminate.

Optional polymer layer 113 can include one or more polymer components, such as those described above for polymer layer 18 . Polymer layer 113 can have any desired thickness. In a non-limiting embodiment, the polymer layer 113 can have a thickness greater than 100 angstroms, such as greater than 500 angstroms, such as greater than 1000 angstroms, such as greater than 1 mm, such as greater than 10 mm, such as between 100 angstroms and 10 mm. The polymer layer 113 can be a permanent layer (ie, not intended to be removed) or can be a temporary layer. "Temporary layer" means a layer that is intended to be removed in a subsequent processing step by methods such as, but not limited to, burning or washing with a solvent. Polymer layer 113 can be formed by any conventional method.

Monolithic article 100 is particularly useful as an automotive transparency. The term "automotive transparency" as used herein refers to automobile side windows, rear windows, moonroofs, sunroofs, and the like. The "transparency" can have a visible light transmittance of any desired amount, eg, 0%-100%. For the visual viewing area, the visible light transmittance is preferably greater than 70%. For areas where vision cannot be observed, the visible light transmission can be lower than 70%.

If only the ply 102 with the functional coating 108 is used as an automotive transparency such as a side window, the low-emissivity functional coating 108 will reduce the solar energy entering the vehicle and also facilitate the trapping of heat energy inside the vehicle. greenhouse effect. The protective coating 110 of the present invention protects by providing a functional coating 108 with a low emissivity (e.g., an emissivity of 0.1 or less) on one side of the coating stack 112 and a high emissivity on the other side. A coating stack 112 of coating 110 (eg, emissivity of 0.5 or greater) is used to overcome this problem. The solar reflective metallic layer in the functional coating 108 reduces solar energy entering the interior of the vehicle, while the high emissivity protective coating 110 reduces the greenhouse effect and allows thermal energy to be removed from the interior of the vehicle. Additionally, layer 110 (or layer 17) can be sunlight absorbing in one or more of the UV, IR and/or visible regions of the electromagnetic spectrum.

3, the article 100 can be placed in an automobile with the protective coating 110 facing the first side 114 of the automobile and the ply 102 facing the second side 116 of the automobile. If the first side is facing the exterior of the vehicle, the coating stack 112 will reflect solar energy due to the presence of the reflective layer in the functional coating 108 . However, due to the high emissivity of the coating stack 112, eg, greater than 0.5, at least some of the thermal energy will be absorbed. The higher the emissivity of the coating stack 112, the more thermal energy will be absorbed. In addition to providing increased emissivity to coating stack 112, protective coating 110 also protects less durable functional coating 108 from mechanical and chemical damage. The optional polymer layer 113 may also provide mechanical and/or chemical stability.

Alternatively, if the first side 114 faces the vehicle interior, the article 100 still provides solar reflective properties due to the metal layer in the functional coating 108 . However, the presence of the protective coating 110 reduces thermal reflectivity by absorbing thermal energy, thereby preventing thermal energy from heating the interior of the vehicle raising its temperature, and thereby reducing the greenhouse effect. Thermal energy from the interior of the vehicle is absorbed by the protective coating 110 and is not reflected back to the interior of the vehicle.

While particularly useful for automotive transparencies, the coating stacks of the present invention should not be considered limited to automotive applications. For example, the coating stack can be introduced into a common insulating glass (IG) unit, eg can be provided on a surface (inner or outer) of one of the glass sheets constituting the IG unit. If on the inner surface in the air space, the coating stack is not necessarily as mechanically and/or chemically durable as it is on the outer surface. Additionally, the coating stack can be used in seasonally adjustable windows, as disclosed in US Patent No. 4,081,934. If on the exterior surface of the window, the protective coating should be of sufficient thickness to protect the functional coating from mechanical and/or chemical damage. The invention can also be used as a monolithic window.

The following examples illustrate the invention, however, they are not to be considered as limiting the invention to their detailed description. All parts and percentages in the following examples and throughout the specification are by weight unless otherwise indicated.

Example

Several samples of functional coatings with different protective coatings of the present invention were prepared and tested for durability, diffuse haze after Taber abrasion, and emissivity. The functional coating is not optimized for mechanical or optical properties but is simply used to illustrate relevant properties, for example, durability, emissivity and/or haze of a functionally coated substrate with the protective coating of the present invention. Methods of making such functional coatings have been described, for example, but not limited to, in US Patent Nos. 4,898,789 and 6,010,602.

Samples were produced by overcoating the different functional coatings described below (on plain soda lime clear glass) with a protective coating of alumina incorporating the structural features of the present invention and having a thickness of 300 Angstroms-1.5 microns. The functional coating used in this experiment has high solar infrared reflectivity and characteristically low emissivity and is a multilayer obtained by depositing alternating layers of zinc stannate and silver by magnetron sputtering vacuum deposition (MSVD). Interference film composition. For the samples discussed below, typically two silver layers and three zinc stannate layers were present in the functional coating. A thin titanium primer is also used in the functional coating on the surface of the silver layer to protect the silver layer from oxidation during MSVD deposition of the zinc oxide stannate layer and to withstand the stresses of bending glass substrates. used heating. The two functional coatings used in the following examples differ mainly in the outermost thin layer of the multilayer coating, one being metallic Ti and the other being the oxide _TiO2 . The thickness of the Ti or _TiO2 outer layer is 10 angstroms to 100 angstroms. Alternative embodiments that are also applicable but not prepared are functional coatings without Ti or _TiO2 outer layers or different metal or oxide outer layers. The functional coating for the example with a thin Ti outer layer has a blue reflection color after heating, while the _TiO2 outer layer has a green reflection color after heating. Other reflective colors of the functional coating after heating that can be protected with the protective coating of the present invention can be achieved by varying the thickness of the respective silver and zinc stannate layers in the functional coating.

Thin or thick alumina protective coatings of the following examples were reactively sputtered by intermediate frequency, bipolar, pulsed dual magnetrons of Al in an Airco ILS1600 (specifically modified to power two of the three targets) to deposit. Power is provided by Advanced Energy (AE) Pinnacle(R) Dual DC power supplies and Astral(R) switching accessories, which convert DC power to bipolar, pulsed power. Glass substrates with functional coatings were introduced into an Airco ILS 1600 MSVD coater with an oxygen-reactive reactive oxygen/argon atmosphere. The two aluminum cathodes are sputtered for different times in order to obtain different thicknesses of aluminum oxide coatings on top of the functional coating.

Three sample blocks (Samples A-C) were prepared and evaluated as follows:

Sample A - 4 inch by 4 inch (10 cm by 10 cm) sheet of 2 mm thick clear float glass commercially available from PPG Industries, Inc. of Pittsburgh, PA.

Sample B - of an experimental low-emissivity functional coating of approximately 1600 angstrom thickness with a green reflective color produced by MSVD (as described above) and of a 2mm thick clear glass coupon with a protective aluminum oxide overcoat A 4 inch by 4 inch (10 cm by 10 cm) test piece was used as a control sample.

Sample C - has _an experimental functional coating produced by MSVD with a blue reflective color, approximately 1600 angstroms thick but further has a 1.53 micron thick aluminum oxide ( _Al2O3 ) protection of the present invention deposited on the functional coating 4 inch by 4 inch (10 cm by 10 cm) pieces of coated 2 mm thick glass coupons.

Duplicate samples A-C were then tested according to the standard Taber abrasion test (ANSI/SAE 26.1-1996) and the results are shown in Figure 4. Scratch density (SD) measurements after a given number of cycles of the Taber test were determined by microscopic measurement of the total scratch length of all scratches in a square micron area using digitization and image analysis software. Sample C (protective coating) coupons showed a lower scratch density than Sample B (functional coating) coupons. Sample C coupons have approximately the same durability as the uncoated glass coupons of Sample A. Taber results were obtained for "as deposited" protective coatings, meaning that the coated glass samples were not post-heated after MSVD deposition of the protective coating. It is expected that the scratch density results should improve after heating of the coated substrate due to the increased density of the heated coating stack (ie, the scratch density should drop for fewer Taber cycles). For example, the coated substrate can be heated from ambient temperature to a maximum temperature in the range of 640°C to 704°C and cooled over a period of about 10 mins to about 30 mins.

Figure 5 shows the mean scattered light haze versus the Taber period (according to ANSI/SAE 26.1-1996) for replicate samples A and C as described above. Sample A is uncoated glass used as a control. The results showed that after 1000 cycles Sample C produced a haze of approximately 2%, the minimum acceptable value as specified by ANSI for the safety of automotive glazing. A modest improvement in the durability of the protective coating is expected to result in less than 2% haze after 1000 Taber cycles, exceeding ANSI safety regulations for automotive glazing.

Figure 6 shows the effect of the inventive overcoat coating deposited on two different functional coatings at different MSVD process vacuum pressures. The sample shown in Figure 6 is a 2 mm thick specimen of clear float glass having deposited on the surface the following coatings:

Sample D - Control sample; nominally 1600 angstrom thickness blue reflective functional coating with no protective coating.

Sample e - control sample; nominally 1600 angstrom thick green reflective functional coating with no protective coating.

Sample F(HP) - functional coating of sample D plus a protective coating of aluminum oxide sputter deposited as described above under 8 microns of oxygen and argon MSVD process vacuum pressure.

Sample F(LP) - functional coating of sample D plus a protective coating of aluminum oxide sputter deposited as described above under 4 micron MSVD process vacuum pressure in oxygen and argon.

Sample G (HP) - Functional coating of Sample E plus a protective coating of aluminum oxide sputter deposited as described above under 8 microns of oxygen and argon MSVD process vacuum pressure.

Sample G(LP) - functional coating of sample E plus a protective coating of aluminum oxide sputter deposited as described above under 4 micron MSVD process vacuum pressure of oxygen and argon.

As shown in Figure 6, as the thickness of the protective coating increases, the emissivity of the coating stack increases. The coating stack has an emissivity greater than about 0.5 at a protective coating thickness of about 1.5 microns.

Figure 7 shows the results of scratch density measurements after 10 cycles of the Taber abrasion test for samples F(HP), F(LP), G(HP) and G(LP) as described above. Control functional samples D and E without a protective coating had an initial scratch density of approximately 45 mm ⁻¹ to 50 mm ⁻¹ . As shown in FIG. 7, application of the protective coating of the present invention (even perhaps below about 800 angstroms) improves the durability of the formed coating stack.

Figure 8 shows the results of scratch density measurements after 10 cycles of the Taber abrasion test for the following samples of blue or green reflective functional coatings with aluminum oxide protective coatings with thicknesses of 300 angstroms, 500 angstroms and 700 angstroms:

Sample H - Functional coating of Sample D plus a protective coating of alumina sputter deposited by MSVD as described above.

Sample I - Functional coating of Sample E plus a protective coating of alumina sputter deposited by MSVD as described above.

As shown on the right side of Figure 8, heating the coating stack of the present invention improves the durability of the coating stack. The coating shown on the right side of Figure 8 was inserted into a 1300°F oven for 3 minutes, then removed and placed into a 400°F oven for 5 minutes, after which the coated samples were removed and tested at ambient conditions. cool down.

Those skilled in the art will readily recognize that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. For example, although in the preferred embodiment of the laminate only one ply includes a functional coating, it should be understood that the present invention may also be used with two plies having a functional coating or one ply having a functional coating and Another layer with a non-functional coating such as a photocatalytic coating is implemented. Additionally, those skilled in the art will recognize that the preferred operating parameters described above can be adjusted for different substrates and/or thicknesses, if desired. Accordingly, the particular embodiments described in detail herein are illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalents thereof.

Claims (44)

1. laminated product comprises:

First base material with first main surface;

The functional coat that at least a portion on the first main surface, forms, wherein this functional coat comprises filming of at least a containing metal oxide compound and at least a infrared external reflection metallic membrane;

The supercoat that at least a portion of functional coat, forms, wherein supercoat comprises the mixture of aluminum oxide and silicon-dioxide, wherein supercoat has the thickness between 100 dusts to 5 micron and wherein functional coat and supercoat constitute the coating stacked body;

Second base material; With

Polymer materials between the supercoat and second base material, wherein the difference between the refractive index of refractive index that supercoat had and polymer materials is within ± 0.2.

2. according to the desired goods of claim 1, wherein at least a in first and second base materials is to be selected from glass, plastics, metal, pottery and their binding substances.

3. according to the desired goods of claim 1, wherein these goods are automobile Transparent Parts.

4. according to the desired goods of claim 1, wherein this functional coat has the emittance between greater than 0 to 0.1.

5. according to the desired goods of claim 1, wherein supercoat brings up at least 0.3 with the emittance of coating stacked body.

6. according to the desired goods of claim 1, wherein the difference between the refractive index of refractive index that supercoat had and polymer materials is within ± 0.1.

7. according to the desired goods of claim 1, wherein polymer materials comprises and is selected from polyvinyl resin, urethane, polyester, at least a polymkeric substance in acrylic resin and the epoxy polymer.

8. according to the desired goods of claim 1, wherein supercoat has uneven thickness.

9. according to the desired goods of claim 1, wherein first and second base materials comprise glass, and this functional coat comprises the control coating at sunshine, and this polymer materials comprises polyvinyl butyral acetal, and supercoat has the refractive index in 1.5 ± 0.1 scopes.

10. according to the desired goods of claim 1, wherein supercoat comprise 15wt% to 70wt% aluminum oxide and 85wt% to 30wt% silicon-dioxide.

11. according to the desired goods of claim 1, wherein supercoat is included in the first layer that forms on the functional coat and the second layer that forms on the first layer, wherein the first layer comprises that the aluminum oxide and the second layer comprise the mixture of silicon-dioxide and aluminum oxide.

12. according to the desired goods of claim 11, wherein the first layer comprises 70wt% aluminum oxide at least.

13. according to the desired goods of claim 12, wherein the first layer has the thickness between 50 dusts to 1 micron.

14. according to the desired goods of claim 13, wherein the first layer has the thickness between 100 dust to 250 dusts.

15. according to the desired goods of claim 11, wherein the second layer comprises 70wt% silicon-dioxide at least.

16. according to the desired goods of claim 15, wherein the second layer has at 50 dusts to 2, the thickness between 000 dust.

17. according to the desired goods of claim 16, wherein the second layer has the thickness between 300 dust to 500 dusts.

18. the monoblock goods comprise:

Base material;

The functional coat that at least a portion of base material, forms;

The supercoat that at least a portion of functional coat, forms, wherein functional coat and supercoat constitute the coating stacked body, wherein this supercoat comprises the layer of the mixture that contains aluminum oxide and silicon-dioxide, and wherein supercoat has thickness between 100 dusts to 5 micron; With

The polymer materials that at least a portion of supercoat, forms,

Wherein supercoat has identical with the refractive index of polymer materials basically refractive index.

19. according to the desired goods of claim 18, wherein these goods are automobile Transparent Parts.

20. according to the desired goods of claim 18, wherein this functional coat has the emittance below 0.1 or 0.1.

21. according to the desired goods of claim 18, wherein supercoat comprise 75wt% to 85wt% aluminum oxide and 15wt% to 25wt% silicon-dioxide.

22. according to the desired goods of claim 18, wherein supercoat has the thickness between 1 micron to 5 microns.

23. according to the desired goods of claim 18, wherein the difference between the refractive index of refractive index that supercoat had and intermediate layer material is within ± 0.2.

24. according to the desired goods of claim 18; wherein supercoat is included in the first layer that forms on the functional coat and the second layer that forms on the first layer; wherein the first layer comprises that 50wt% aluminum oxide and the second layer at least comprise the mixture of silicon-dioxide and aluminum oxide.

25. according to the desired goods of claim 24, wherein the first layer comprises 70wt% aluminum oxide at least.

26. according to the desired goods of claim 25, wherein the first layer has the thickness between 50 dusts to 1 micron.

27. according to the desired goods of claim 26, wherein the first layer has the thickness between 100 dust to 250 dusts.

28. according to the desired goods of claim 24, wherein the second layer has at 50 dusts to 2, the thickness between 000 dust.

29. according to the desired goods of claim 28, wherein the second layer has the thickness between 300 dust to 500 dusts.

30. according to the desired goods of claim 18, wherein this polymer materials comprises polyvinyl butyral acetal.

31. according to the desired goods of claim 18, wherein supercoat has uneven thickness.

32. laminated product comprises:

First base material with first main surface;

The functional coat that at least a portion on the first main surface, forms;

The supercoat that at least a portion of functional coat, forms, they have constituted the coating stacked body, and wherein supercoat is the laminated coating of the second layer that comprises the first layer that contains aluminum oxide and contain the mixture of aluminum oxide and silicon-dioxide;

Second base material; With

Polymer materials between first and second base materials, wherein supercoat has identical with the refractive index of polymer materials basically refractive index.

33. make the method for laminated product, may further comprise the steps:

First base material is provided;

On at least a portion of first base material, provide functional coat;

Provide supercoat at least a portion of functional coat, this supercoat comprises the layer of the mixture that contains aluminum oxide and silicon-dioxide; With

At least a polymer materials is provided at least a portion of supercoat,

Wherein supercoat and polymer materials are selected, made this supercoat and polymer materials have substantially the same refractive index.

34. according to the desired method of claim 33, wherein this polymer materials comprises that polyvinyl butyral acetal and supercoat comprise that 35wt% aluminum oxide and supercoat at least have 1.5 ± 0.2 refractive index.

35. according to the desired method of claim 33, wherein supercoat is a laminated coating, it comprises: comprise the first layer of aluminum oxide and comprise silicon-dioxide and the second layer of the mixture of aluminum oxide.

36. according to the desired method of claim 33, wherein supercoat has the thickness between 100 dusts to 5 micron.

37. according to the desired method of claim 33, comprising: second base material is provided; With utilize polymer materials that first and second substrate layers are forced together.

38. make the method for laminate substrate, may further comprise the steps:

First base material is provided;

On at least a portion of first base material, form functional coat; With

On at least a portion of functional coat, form supercoat; wherein supercoat is included in the first layer that forms on the functional coat and the second layer that forms on the first layer; wherein the first layer comprises that 50wt% aluminum oxide and the second layer at least comprise the mixture of silicon-dioxide and aluminum oxide.

39. according to the desired method of claim 38, wherein the first layer has the thickness between 50 dusts to 1 micron.

40. according to the desired method of claim 39, wherein the first layer has the thickness between 100 dust to 250 dusts.

41. according to the desired method of claim 38, wherein the second layer comprises 70wt% silicon-dioxide at least.

42. according to the desired method of claim 41, wherein the second layer has at 50 dusts to 2, the thickness between 000 dust.

43. according to the desired method of claim 42, wherein the second layer has the thickness between 300 dust to 500 dusts.

44., further comprise according to the desired method of claim 38:

Second base material is provided;

Second base material is positioned on first base material, and functional coat is between above-mentioned base material; With

Heated substrate allows this base material bend to desired shape.

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